CA1320494C - Method of making purely primary diamines - Google Patents
Method of making purely primary diaminesInfo
- Publication number
- CA1320494C CA1320494C CA000568395A CA568395A CA1320494C CA 1320494 C CA1320494 C CA 1320494C CA 000568395 A CA000568395 A CA 000568395A CA 568395 A CA568395 A CA 568395A CA 1320494 C CA1320494 C CA 1320494C
- Authority
- CA
- Canada
- Prior art keywords
- polyether
- formula
- molecular weight
- purely
- omega
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
- C08G65/16—Cyclic ethers having four or more ring atoms
- C08G65/20—Tetrahydrofuran
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
- C08G18/5024—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
Abstract
Abstract The present invention provides a method for making primary amine terminated linear polyethers of molecular weight above about 3500 which have virtually no contamination from in-chain secondary amine functionalities or amine-terminated tertiary amine side-chains. This method involves the production of novel intermediates.
The invention also provides purely linear polyether-polyurea block copolymers formed by chain extension of the primary amine terminated linear polyethers.
The invention also provides purely linear polyether-polyurea block copolymers formed by chain extension of the primary amine terminated linear polyethers.
Description
METHOD OF MAKING PURELY PRIMARY DIAMINES
Technlcal Fleld The present lnventlon relates to a method of maklng polyether dlprl~ary amlnes that are completely free of secondary or tertlary amine functlonallty ln the polymer chaln. The lnventlon also relates to novel precursors for the polyether dlprlmary amlnes, and to polyether-polyurea block copolymers made therefrom.
Thls applicatlon has been dlvlded. Thls parent appllcatlon relates to lntermedlates and the use thereof to prepare dlamlno polyethers.
A dlvlslonal appllcatlon has been flled which relates to block copolymers.
In accordance wlth one aspect of the present parent appllcatlon, there ls provlded a method for preparatlon of purely prlmary a, -dlamlnopolyethers havlng the general formula ' H2N-A-NH2, whereln A ls a polyether molety havlng a molecular welght of at least about 3500 contalnlng recurrlng groups, a ma~or portlon of whlch belng oxytetramethylene units, and a mlnor portlon belng other oxyalkylene unlts havlng up to about 4 stralght chaln carbon atoms, comprlslng the steps of:
a) reactlng a nltrogen-containlng nucleophlle accordlng to the followlng formula~
NX'X2 where X ls a substltuent whlch ls easlly cleaved by hydroxyllc solvents and X' ls selected from the group conslstlng of X and an electron palr, wlth a termlnally electrophlllcally actlve polyether represented by the followlng general formulae:
, ,, ~ ~
=, 2 50557-3g50 ~3 ~
C A - O ~ 2 ~ and Y- A- Y
whereln Y ls a non-nucleophllic molety, and A ls as deflned above;
b) performlng solvolysls on the product of reactlon a); and c) lsolatlng the products thereof.
In accordance wlth another aspect of the parent appllcatlon there ls provlded novel lntermedlates for a purely prlmary a, ~ -dlamlno polyether havlng the followlng formulae:
X N-A-NX ~2 ~ and X2N-A-NX2 where$n X ls a substltuent whlch ls easlly cleaved by hydroxyllc solvents, Y ls a non-nucleophlllc molety and A ls a polyether molety of molecular welght above about 3500 contalnlng recurrlng groups, a ma~or portlon of whlch belng oxytetramethylene unlts, and a mlnor portlon belng other oxyalkylene unlts havlng up to about 4 straight chaln carbon atoms.
In accordance wlth one aspect of the dlvlslonal appllcatlon, there ls provlded a purely llnear polyether-polyurea block copolymer comprlslng a repeatlng unit havlng the general 2~ formula:
O O / O O~
Il Ill 11 11 \
N-Z-N-C-N-A-N-C N-Z-N-C-W-B-W-C-~l l l ~
H H H H ~ H / m whereln:
Z ls a dlvalent radlcal selected from the group conslstlng of phenylene, alkylene, aralkylene, and cycloalkylene~
B ls Relected from the group conslstlng of a dlvalent radlcal 1 3204q4 selected from alkylene, aralkylene, cycloalkylene, and phenylene;
W ls a dlfunctlonal molety selected from -0- and -N- where D ls selected from the group conslstlng of hydrogen, an alkyl radlca~ wlth from one to ten carbon atoms, phenyl and an alkylene radlcal whlch completes a rlng structure lncludlng B to form a heterocycle;
m ls an lnteger from zero to about 25~ and A ls a polyether molety havlng a molecular welght of at least about 3500 contalnlng recurrlng groups, a ma~or portlon belng oxytetramethylene unlts, and a mlnor portlon belng other oxyalkylene unlt~ havlng up to about 4 stralght chaln carbon atoms.
In accordance wlth another aspect of the dlvlslonal appllcatlon there ls provlded a process for preparlng a polyether-polyurea block copolymer comprlslng a repeatlng unlt havlng the general formula:
O O / O
ll 11 / 11 11 \
N-Z-N-C-N-A-N-C N-Z-N-C-W-B-W-C-l l H H H H \ H / m whereln~
Z ls a dlvalent radlcal selected from the group conslstlng of phenylene, alkylene, aralkylene, and cycloalkylene;
B ls a dlvalent radlcal selected from the group conslstlng of alkylene, aralkylene, cycloalkylene, and phenylene;
W ls a dlfunctlonal molety selecte~ from -O- and -N- where ~;
1 3204~4 4 60557-3g50 D ls selected from the group conslstlng of hydrogen, an alkyl radlcal with from one to ten carbon atoms, phenyl, and an alkylene radlcal whlch completes a rlng structure lncludlng B to form a heterocycle;
m ls an lnteger from zero to about 25; and A ls a polyether molety havlng d molecular welght of at least about 3500 contalnlng recurrlng groups, a ma~or portlon belng oxytetramethylene unlts, and a mlnor portlon belng other oxyalkylene unlts havlng up to about 4 stralght chaln carbon 0 atoms, whlch process comprlses a) reactlng a nltrogen-contalnlng nucleophlle accordlng to the followlng formula:
NX'X2 where X ls a substltuent whlch ls easlly cleaved by hydroxyllc solvents and X' ls selected from the group conslstlng of X and an electron palr, wlth a termlnally electrophlllcally actlve polyether represented by the followlng general formulae:
~ - A - O ~ '2Y~ Y - A - Y
whereln Y is a non-nucleophlllc molety, and A ls as deflned above;
b) performlng solvolysls on the product of reactlon a);
c~ lsolatlng a product so formed; and d) polymerlzlng the purely prlmary a, -dlamlno polyether so formed wlth a dllsocyanate of formula IX, OCN-Z-NCO ~IX) where Z ls as deflned above and, where requlred, with a dlamlne or dlol chaln extender of the 4~ 60557-3450 formula VIII, H-W-B-W-H (VIII) whereln W and ~ are as deflned above.
Backaround of the Inventlon Polyethers wlth molecular welghts above 3500 havlng termlnal prlmary amlno functlonallty are an lmportant class of polymers havlng a varlety of uses. These polyethers may be reacted wlth epoxy resins to create tough lnfuslble plastlcs as well as elastomerlc vulcanlzates. Further, these polyethers may be reacted wlth dllsocyanates to create polyurea block copolymers.
It 18 very lmportant for such appllcatlons that the amlne termlnated polyether precursors be as purely difunctlonal as posslble, l.e., have no termlnal hydroxyl, hallde, or other lnert functlonallty, ln order to maxlmlze the degree of polymerlzatlon of the deslred products as well as thelr performance.
U.S. Patent 3,436,359 dlscloses polyether dlamlnes wlth a hlgh degree of termlnal prlmary amlno groups. These polyethers were obtalned by capplng the hlghly difunctlonal bls-oxonlum lons resultlng from the reactlon of cycllc ether monomers and trifluoromethanesulfonlc anhydrlde wlth anhydrous ammonla.
However, lt ls dlfflcult to carry out thls process wlthout obtalnlng polyether dlamlnes contamlnated wlth certain amounts of secondary amlne groups (up to 3%) as well as smaller amounts of tertlary amlno nltrogens (up to 0.3%) ln the chaln whlch provlde a prlmary amlne termlnated polyether branch or slde chaln. It ls especlally dlfflcult to control the level of formatlon of these by-products when the process ls carrled out on a large scale.
;,~ ",. ..
4b 60557-3450 Although such mlxtures are useful ln a number of appllcatlons, polyether dlamlnes contalnlng even these low levels of multlfunctlonal lmpurltles are unsultable for the preparatlon of hlgh molecular welght soluble polyether-polyurea block copolymers from the reactlon of polyether dlamlnes wlth stolchlometrlc molar ratlos of dllsocyantes. These ln-chaln secondary amlnes and prlmary amlne termlnated tertlary slde chalns provlde addltlonal sltes on the polymer chaln whlch result ln crossllnklng upon reactlon wlth dllsocyanates. Thls typlcally results ln unprocessable gels.
There ls now dlsclosed a method for maklng prlmary amlne-termlnated linear polyethers of the deslred molecular welght range whlch have vlrtually no contamlnatlon from ln-chaln secondary amlne functlonalltles or amlne-termlnated tertlary amlne slde-chains, even when carrled out on a large scale. Thls method lnvolves the productlon of novel lntermedlates.
Dlamlno polyethers made by the present process have the general formula:
Formula I
whereln A ls a polyether molety of molecular welght above about 3500 contalnlng recurrlng groups, a ma~or portlon conslstlng of oxytetramethylene unlts, and at most a mlnor portlon conslstlng of other oxyalkylene unlts, the alkyl portlons thereof havlng up to about 4 stralght chaln carbon atoms.
The method comprlses reactlng a nltrogen-contalnlng nucleophlle accordlng to the formula, NX'X2, where X ls a substltuent whlch ls easlly cleaved by hydroxyllc solvents and X' qc 60557-3450 is selected from the group conslstlng of X and an electron palr, wlth a termlnally electrophllically-actlve polyether accordlng to the followlng general formulae:
C 0-A-0~ ~2 ~ Y-A-Y
Formula II Formula III
whereln Y ls a non-nucleophlllc molety and A ls deflned above.
Solvolysls ls then performed on the product of thls reactlon, and lt ls lsolated by conventlonal technlques.
Polymerlzatlon of tetrahydrofuran (or tetrahydrofuran plus a mlnor amount of one or more catlonlcally polymerlzable cycllc ethers havlng from 2 to about 4 rlng carbon atoms) wlth a superacld anhydrlde (such as trlfluoromethanesulfonlc anhydrlde) followed by termlnatlon of the resultlng dl-catlonlcally actlve llnear polyethers by reactlon wlth sultable nltrogen-contalnlng nucleophlles, provldes novel lntermedlates wlth the followlng general formulae:
X3 ~-A-~ X~- 2 ~ X2~-A-NX2 Formula IV Formula V
whereln X and A are as deflned above. Sultable nitrogen-contalnlng nucleophlles are those havlng no actlve hydrogens.
Solvolysls of the novel lntermedlates provldes the purely prlmary dlamlno-termlnated polyethers. Chaln-extenslon of these polyethers then provldes the purely llnear polyether-polyurea block copolymers.
There ls dlsclosed a method for the preparatlon of purely prlmary dlamlno polyethers of Formula I:
4d 60557-3450 Formula I
where A ls a polyether molety of molecular welght above about 3500 contalning recurrlng groups, a ma~or portlon conslstlng of oxytetramethylene unlts, and at most a mlnor portlon conslstlng of other oxyalkylene unlts, the alkyl portlons thereof havlng up to about 4 stralght chaln carbon atoms. Preferably, A conslsts excluslvely of oxytetramethylene unlts. Preferred dlamlno polyethers are a- ~-dlamlnopolytetramethylene oxldes havlng the followlng formula: / \
H2N ~ '~ '~~NH2 n Formula IA
whereln n ls an lnteger of at least about 50, preferably from about 140 to about 280.
The method conslsts of the hydrolysls or, preferably, methanolysls of the novel lntermedlates represented by Formulas IV
and V;
X ~-A-~NX ' 2 ~ X2N-A-NX2 Formula IV Formula V
where X ls a substltuent whlch ls readlly cleaved wlth hydroxyllc solvent such as water or, preferably, methanol to provlde the free amlne, and A ls as deflned above.
The novel intermediates of Formulas IV and V are made by reacting terminally electrophilically active polyethers corresponding to Formulas II and III:
Cd~ -- A --(3C~1 ' 2~ Y -- A -- Y
Formula II Formula III
where A is as defined above and wherein Y is a 10 non-nucleophilic moiety such as a trifluoromethanesulfonoxy group, a fluorosulfonoxy group, phosphorus hexafluoride, and the like, with a nitrogen nucleophile that has no active hydrogens. This nucleophile can be represented by Formula VI:
NX'X2 Formula VI
where X is a substituent which is easily cleaved by 20 hydroxylic solvents such as water or, preferably, methanol to provide the free amine; x~ may be the same as x or may be a pair of electrons to provide a negative charge. The polyethers of Formulas II and III are prepared by polymerization of tetrahydrofuran (or tetrahydrofuran plus up 25 to about 40 mole percent of one or more cationically polymerizable comonomeric cyclic ethers having from 2 to about 4 ring carbon atoms) with a superacid anhydride such as trifluoromethanesulfonic anhydride. ~xamples of cationically polymerizable cyclic ether comonomers include 30 3-methyltetrahydrofuran, 2-methyltetrahydrofuran, ethylene oxide, oxacyclobutane, and the like.
In order to obtain polyether amines by the method 'h^ procont in:~ntion~ the highly difunctional bis-electrophilically active polymer of Formula II or III is reacted with a suitable nitrogen containing nucleophile of Formula VI. This provides the novel intermediates of Formulas IV and V. Suitable nucleophiles are those which have no N-H
bonds. Utilizing such nucleophiles entirely eliminates the possibility of forming undesired secondary or tertiary amine in-chain moieties. The nucleophiles should also be reasonably soluble in non-hydroxylic solvents. The X groups, as stated 5 above, should be substituents which are readily cleaved with a solvent, such as water or, preferably, methanol, to provide the primary amine moiety, -NH2. Finally, the X substituent should be obtained in such a state as to be easily and completely removed from the diamino polyether endproduct.
Preferable nucleophiles include hexamethylene-tetramine and alkali metal salts of hexamethyldisilazane. The lithium salt is particularly preferred. Use of these nucleophiles result in the novel intermediates having the Formulas IVA and VA as depicted below:
N3(CH2)6N-A-N(CH2)6N3-2 Formula IVA
(Me3Si)2N-A-N(SiMe3)2 Formula VA
Cleavage of these intermediates to desired diprimary amines occurs readily upon heating with methanol, 25 or methanol and sulfuric acid. The byproducts of the methanolysis, dimethoxymethane and methoxytrimethylsilane, respectively, are highly volatile and easily distilled from the polymer solution.
The polyether diamines obtained by the method 30 ~b~ Rv-Rt~n are highly pure. High molecular weight polyether-polyurea block copolymers may be produced from the reaction of these diamines with various diisocyanates in stoichiometric molar ratios without gellation caused by crosslinking due to the presence of multifunctional 35 impurities. Preferred diisocyanates include toluene diisocyanate, hexamethylene diisocyanate, 4,4'-methylene-bis(phenylisocyanate), 4,4'-methylene-bis(cyclohexyl-isocyanate), and isophorone diisocyanate.
Preferred solvents for the chain extension reaction are those which are unreactive with isocyanates and which maintain both the reactants and the products in solution.
Preferred solvents include ethers, chlorinated hydrocarbons, S certain alcohols, and mixtures thereof. Most preferred solvents include methylene chloride, tetrahydrofuran and isopropanol.
Polyether-~olyurea block copolymers created by chain extension ofAdiprimary amines made by the method 10 thi~ inv~nt-ion are purely linear, and comprise a repeating unit represented by Formula VII as depicted below:
O O / O O~
li 11 11 11 N--Z--N-C- I_A_N_C N-Z- I_C_W_B_W_C
H H H H H H J
Formula VII
wherein:
20 Z is a divalent radical selected from phenylene, alkylene, aralkylene, and cycloalkylene; preferably Z is methylene dicyclohexylene, hexamethylene and methylene cyclohexylene;
B is a divalent radical selected from alkylene, aralkylene, cycloalkylene, and phenylene;
25 W is a difunctional moiety selected from -O- and -N- where D is hydrogen, an alkyl radical with from one to ten carbon atoms, phenyl, or an alkylene radical which completes a ring structure including B to form a heterocycle;
30 m is an integer from zero to about 25, preferably from about 2 to about 10; and A is as defined above.
The polymers are made by polymerizing in an inert atmosphere the exceptionally pure polyether diamine of 35 Formula I, optional diamine or diol chain extender having a molecular structure represented by Formula VIII:
~ w-~--w--i~
Fo rmula VI I I
5 where W and ~ are as defined above, and a stoichiometric amount of diisocyanate having a molecular structure represented by Formula IX:
OCN-Z-NCO
Fo rmula IX
where Z is as described above.
The combined molar ratio of polyether diamine and 15 diamine or diol chain extender to diisocyanate in the reaction is that which will provide useful properties in the final product, preferably about 1:0.95 to about 1:1.05.
The resulting polyether polyurea block copolymers are purely linear, high molecular weight, soluble elastomers 20 with outstanding properties. Such elastomers have many applications which are well known in the art. For a detailed discussion, see Polyurethanes: Chemistry and Technology, Part II, Saunders, J. ~. and Frisch, K.C., Interscience, NY 1964, pp. 431-447. Depending on the particular application, the 25 elastomeric properties can be varied significantly by the choice of molecular weight of the polyether diamine and, especially, by the incorporation of various low molecular weight chain extenders such as hexamethylene diamine, xylylene diamine, piperazine, and the like, with 30 1,3-di(4-piperidyl) propane being most preferred.
The following examples are intended to be illustrative only, and should not be construed as limiting the invention.
35Example 1 A 500 ml three-necked round bottom flask was charged with 125 g dry tetrahydrofuran and 25 g methylene ~ 3~0~ 94 chloride. The solution was cooled to 12C, and, with mechanical stirring, 3.3 g trifluoromethanesulfonicanhydride in 25 g methylene chloride was added rapidly via syringe.
After an exotherm to 21C, the reaction was cooled to 12C
and stirred at that temperature for 2.0 hours. The stirrer was stopped, and a slurry of 4.1 g hexamethylene tetramine in 25 g chloroform was added. The stirrer was started and run at high speed for 1/2 hour at room temperature. A solution of 9.3 g concentrated H2 S04 in 60 g methanol and 60 g toluene was added, the reaction was equipped with a distilling head, and the volatiles were distilled while replenishing the system with methanol until the pot temperature remained at 65C for one hour. A solution of 2.1 g hydroxylamine sulfate in 6 ml water was added and the reaction heated under reflux for an hour. The solution was then cooled to about 30C, and 29.0 g 50~ NaOH was added with stirring. The mixture was heated, and the MeOH and other volatiles were allowed to distill while replenishing the pot with toluene. At a pot temperature of 80C, 4.1 g solid NaHCO3 was added and the distillation continued until the pot reached 108C. The mixture was cooled to about 60-70C and filtered through a layer of a filter aid such as diatomaceous earth, available from Johns-Manville under the tradename Super Cel~, washing the collected salts with toluene. The combined filtrate and 25 washings were stripped to dryness on a rotary evaporator to provide 79.6 g (64%) polytetramethylene oxide diprimary amine as a clear, colorless, viscous oil which solidified on standing at room temperature. Titration of a sample in isopropanol-tetrahydrofuran solution with 0.1 N HCl to a bromphenol blue endpoint gave a molecular weight of 9,734.
Example 2 To a 1,000 ml three-necked round bottom flask under dry nitrogen was added 150 g dry tetrahydrofuran and 26.4 g cyclohexane. While stirring mechanically, 3.45 g (CF3SO2)20 was added rapidly via syringe at room temperature. The temperature was allowed to rise to 30C, and then the stirred ~f~ r1~
reaction was cooled to 15~C and held at that temperature for a total of 2 1/2 hours. At that time, 25 ml of a 1.0 M
solution of lithium bis(trimethylsilyl)amide in hexane was added rapidly via syringe. The temperature rose to 21C, the mixture was stirred at room temperature for 1/2 hour, and then diluted to 800 ml with toluene and 100 ml methanol. The reaction flask was fitted for distillation and the volatiles collected to a pot temperature of 110C while keeping the volume constant by the continued addition of toluene. The resulting solution, containing a precipitate of lithium trifluoromethanesulfonate, was cooled to 50-60C and filtered through a pad of Super CelR filter material which was washed with additional toluene. The combined filtrate and washings were stripped to dryness on a rotary evaporator to give polytetramethylene oxide diprimary amine as a pale yellow viscous oil which solidified to a cream colored solid on standing. The yield was 97.5 g (65%). Titration with 0.1 N HCl gave a molecular weight of 11,000.
Example 3 A 75 gallon stainless steel reactor was charged with 90.7 kg dry tetrahydrofuran and cooled to 16C with agitation. A solution of 1.5 kg trifluoromethanesulfonic anhydride in 6.8 kg of cyclohexane was added rapidly with stirring. Transfer was completed with an additional 6.8 kg of cyclohexane. The reaction exothermed to 32C and was then heated to 43C and held at this temperature for 1/2 hour. The reaction was cooled to 18-21C for an additional 2.5 hours.
The viscous, clear solution was treated as rapidly as possible with 13.3 kg of a 20% solution of lithium bis(trimethyl silyl) amide in hexane. The reaction exothermed to 27C and was allowed to stir for l/2 hour. Toluene (113.4 kg) and methanol (15.5 kg) were charged to the reactor and the heating jacket set to 88C. Volatiles were allowed to 35 distill over a two hour period. The jacket temperature was then raised to 149C and the distillation continued until the contents reached 104C. The solution was cooled to 32C;
45.q kg of heptane and 6.8 kg of Super Cel~ filter material were added. After stirring for 1/2 hour, the mixture was filtered and the filtrate returned to the kettle. A total of 83.9 kg of volatiles were distilled. The resulting solution 5 was cooled to room temperature to provide polytetramethylene oxide diprimary amine as a 50% solids solution. The total yield of polymer was 63.5 kg (70% yield) and had a titrated molecular weight of 16,000.
Example 4 To a 1,000 ml three-necked round bottom flask under dry nitrogen was added 135 g dry tetrahydrofuran, 13.8 g 3-methyl tetrahydrofuran, and 26.4 g cyclohexane. While stirring mechanically, 3.47 g (CF3 S2 )2 was added rapidly 15 via syringe at 10C. The temperature was allowed to rise to 40C, and then the reaction was stirred for 1/2 hour, cooled to 15C, and held at that temperature for a total of 2 hours.
At that time, 25 ml of a 1.0 M solution of lithium bis(trimethylsilyl)amide in hexane was added rapidly via 20 syringe. The temperature rose to 28C, the mixture was stirred at room temperature for 1/2 hour, and then diluted with 200 ml of toluene. The reaction flask was fitted for distillation and the volatiles collected to a pot temperature of 110C while keeping the volume constant by the continued 25 addition of toluene. The resulting solution, containing a precipitate of lithium trifluoromethanesulfonate, was cooled to 22C and 178 g of heptane added before filtering through a pad of Super Cel~ filter material which was washed with additional toluene. The combined filtrate and washings were 30 concentrated to 30% solids w/w. Then, 125 g of methanol was added, and the solution was heated to 105C while allowing the methanol and other volatiles to distill. The resultant solution was stripped to dryness on a rotary evaporator to give polyether diprimary amine as a pale yellow viscous oil 35 which solidified to a cream colored solid on standing. The yield was 112.5 g (76%). Titration with 0.1 N HCl gave a molecular weight of 11,853.
Example 5 A solution of 8.33 g of 8,333 molecular weight polytetramethylene oxide diprimary amine (1.0 mmol) and 5 0.288 g 2,5-dimethylpiperazine (1.0 mmol) in 65 g isopropanol and 35 g methylene chloride was stirred and treated with 0.786 g (2.0 mmol) of 4,4'-methylene bis(cyclohexyl-isocyanate) (H-MDI). In 15 minutes at room temperature, the viscosity had risen dramatically, but the solution remained 10 clear and did not gel. A film was cast to provide, after solvent evaporation, a clear, strong polyether polyurea elastomer film having the following properties:
Tensile - 8,155 psi Elongation - 660 Permanent Set - 12~
A film is completely soluble in solvents such as chloroform, toluene, isopropanol, and tetrahydrofuran.
Example 6 To a solution of 10.08 g of the polyether diprimary amine of Example 4 (11,853 molecular weight; 0.85 mmol) in 30 ml of methylene chloride at room temperature was added all at once with rapid stirring a solution of 0.76 g of isophorone diisocyanate (3.42 mmol). The resulting solution 25 was treated dropwise with stirring with a solution of 0.54 g 1,3-bis(4-piperidyl) propane (2.57 mmol) in 30 ml of methylene chloride. Toward the end of the addition, the reaction became quite viscous but remained clear. The contents of the flask were cast onto a glass plate and the 30 solvent allowed to evaporate. The resulting polyether-polyurea block copolymer was obtained as a clear, strong elastomeric film having the following properties:
Tensile - 5600 psi Elongation - 700%
Permanent Set - 35%
Technlcal Fleld The present lnventlon relates to a method of maklng polyether dlprl~ary amlnes that are completely free of secondary or tertlary amine functlonallty ln the polymer chaln. The lnventlon also relates to novel precursors for the polyether dlprlmary amlnes, and to polyether-polyurea block copolymers made therefrom.
Thls applicatlon has been dlvlded. Thls parent appllcatlon relates to lntermedlates and the use thereof to prepare dlamlno polyethers.
A dlvlslonal appllcatlon has been flled which relates to block copolymers.
In accordance wlth one aspect of the present parent appllcatlon, there ls provlded a method for preparatlon of purely prlmary a, -dlamlnopolyethers havlng the general formula ' H2N-A-NH2, whereln A ls a polyether molety havlng a molecular welght of at least about 3500 contalnlng recurrlng groups, a ma~or portlon of whlch belng oxytetramethylene units, and a mlnor portlon belng other oxyalkylene unlts havlng up to about 4 stralght chaln carbon atoms, comprlslng the steps of:
a) reactlng a nltrogen-containlng nucleophlle accordlng to the followlng formula~
NX'X2 where X ls a substltuent whlch ls easlly cleaved by hydroxyllc solvents and X' ls selected from the group conslstlng of X and an electron palr, wlth a termlnally electrophlllcally actlve polyether represented by the followlng general formulae:
, ,, ~ ~
=, 2 50557-3g50 ~3 ~
C A - O ~ 2 ~ and Y- A- Y
whereln Y ls a non-nucleophllic molety, and A ls as deflned above;
b) performlng solvolysls on the product of reactlon a); and c) lsolatlng the products thereof.
In accordance wlth another aspect of the parent appllcatlon there ls provlded novel lntermedlates for a purely prlmary a, ~ -dlamlno polyether havlng the followlng formulae:
X N-A-NX ~2 ~ and X2N-A-NX2 where$n X ls a substltuent whlch ls easlly cleaved by hydroxyllc solvents, Y ls a non-nucleophlllc molety and A ls a polyether molety of molecular welght above about 3500 contalnlng recurrlng groups, a ma~or portlon of whlch belng oxytetramethylene unlts, and a mlnor portlon belng other oxyalkylene unlts havlng up to about 4 straight chaln carbon atoms.
In accordance wlth one aspect of the dlvlslonal appllcatlon, there ls provlded a purely llnear polyether-polyurea block copolymer comprlslng a repeatlng unit havlng the general 2~ formula:
O O / O O~
Il Ill 11 11 \
N-Z-N-C-N-A-N-C N-Z-N-C-W-B-W-C-~l l l ~
H H H H ~ H / m whereln:
Z ls a dlvalent radlcal selected from the group conslstlng of phenylene, alkylene, aralkylene, and cycloalkylene~
B ls Relected from the group conslstlng of a dlvalent radlcal 1 3204q4 selected from alkylene, aralkylene, cycloalkylene, and phenylene;
W ls a dlfunctlonal molety selected from -0- and -N- where D ls selected from the group conslstlng of hydrogen, an alkyl radlca~ wlth from one to ten carbon atoms, phenyl and an alkylene radlcal whlch completes a rlng structure lncludlng B to form a heterocycle;
m ls an lnteger from zero to about 25~ and A ls a polyether molety havlng a molecular welght of at least about 3500 contalnlng recurrlng groups, a ma~or portlon belng oxytetramethylene unlts, and a mlnor portlon belng other oxyalkylene unlt~ havlng up to about 4 stralght chaln carbon atoms.
In accordance wlth another aspect of the dlvlslonal appllcatlon there ls provlded a process for preparlng a polyether-polyurea block copolymer comprlslng a repeatlng unlt havlng the general formula:
O O / O
ll 11 / 11 11 \
N-Z-N-C-N-A-N-C N-Z-N-C-W-B-W-C-l l H H H H \ H / m whereln~
Z ls a dlvalent radlcal selected from the group conslstlng of phenylene, alkylene, aralkylene, and cycloalkylene;
B ls a dlvalent radlcal selected from the group conslstlng of alkylene, aralkylene, cycloalkylene, and phenylene;
W ls a dlfunctlonal molety selecte~ from -O- and -N- where ~;
1 3204~4 4 60557-3g50 D ls selected from the group conslstlng of hydrogen, an alkyl radlcal with from one to ten carbon atoms, phenyl, and an alkylene radlcal whlch completes a rlng structure lncludlng B to form a heterocycle;
m ls an lnteger from zero to about 25; and A ls a polyether molety havlng d molecular welght of at least about 3500 contalnlng recurrlng groups, a ma~or portlon belng oxytetramethylene unlts, and a mlnor portlon belng other oxyalkylene unlts havlng up to about 4 stralght chaln carbon 0 atoms, whlch process comprlses a) reactlng a nltrogen-contalnlng nucleophlle accordlng to the followlng formula:
NX'X2 where X ls a substltuent whlch ls easlly cleaved by hydroxyllc solvents and X' ls selected from the group conslstlng of X and an electron palr, wlth a termlnally electrophlllcally actlve polyether represented by the followlng general formulae:
~ - A - O ~ '2Y~ Y - A - Y
whereln Y is a non-nucleophlllc molety, and A ls as deflned above;
b) performlng solvolysls on the product of reactlon a);
c~ lsolatlng a product so formed; and d) polymerlzlng the purely prlmary a, -dlamlno polyether so formed wlth a dllsocyanate of formula IX, OCN-Z-NCO ~IX) where Z ls as deflned above and, where requlred, with a dlamlne or dlol chaln extender of the 4~ 60557-3450 formula VIII, H-W-B-W-H (VIII) whereln W and ~ are as deflned above.
Backaround of the Inventlon Polyethers wlth molecular welghts above 3500 havlng termlnal prlmary amlno functlonallty are an lmportant class of polymers havlng a varlety of uses. These polyethers may be reacted wlth epoxy resins to create tough lnfuslble plastlcs as well as elastomerlc vulcanlzates. Further, these polyethers may be reacted wlth dllsocyanates to create polyurea block copolymers.
It 18 very lmportant for such appllcatlons that the amlne termlnated polyether precursors be as purely difunctlonal as posslble, l.e., have no termlnal hydroxyl, hallde, or other lnert functlonallty, ln order to maxlmlze the degree of polymerlzatlon of the deslred products as well as thelr performance.
U.S. Patent 3,436,359 dlscloses polyether dlamlnes wlth a hlgh degree of termlnal prlmary amlno groups. These polyethers were obtalned by capplng the hlghly difunctlonal bls-oxonlum lons resultlng from the reactlon of cycllc ether monomers and trifluoromethanesulfonlc anhydrlde wlth anhydrous ammonla.
However, lt ls dlfflcult to carry out thls process wlthout obtalnlng polyether dlamlnes contamlnated wlth certain amounts of secondary amlne groups (up to 3%) as well as smaller amounts of tertlary amlno nltrogens (up to 0.3%) ln the chaln whlch provlde a prlmary amlne termlnated polyether branch or slde chaln. It ls especlally dlfflcult to control the level of formatlon of these by-products when the process ls carrled out on a large scale.
;,~ ",. ..
4b 60557-3450 Although such mlxtures are useful ln a number of appllcatlons, polyether dlamlnes contalnlng even these low levels of multlfunctlonal lmpurltles are unsultable for the preparatlon of hlgh molecular welght soluble polyether-polyurea block copolymers from the reactlon of polyether dlamlnes wlth stolchlometrlc molar ratlos of dllsocyantes. These ln-chaln secondary amlnes and prlmary amlne termlnated tertlary slde chalns provlde addltlonal sltes on the polymer chaln whlch result ln crossllnklng upon reactlon wlth dllsocyanates. Thls typlcally results ln unprocessable gels.
There ls now dlsclosed a method for maklng prlmary amlne-termlnated linear polyethers of the deslred molecular welght range whlch have vlrtually no contamlnatlon from ln-chaln secondary amlne functlonalltles or amlne-termlnated tertlary amlne slde-chains, even when carrled out on a large scale. Thls method lnvolves the productlon of novel lntermedlates.
Dlamlno polyethers made by the present process have the general formula:
Formula I
whereln A ls a polyether molety of molecular welght above about 3500 contalnlng recurrlng groups, a ma~or portlon conslstlng of oxytetramethylene unlts, and at most a mlnor portlon conslstlng of other oxyalkylene unlts, the alkyl portlons thereof havlng up to about 4 stralght chaln carbon atoms.
The method comprlses reactlng a nltrogen-contalnlng nucleophlle accordlng to the formula, NX'X2, where X ls a substltuent whlch ls easlly cleaved by hydroxyllc solvents and X' qc 60557-3450 is selected from the group conslstlng of X and an electron palr, wlth a termlnally electrophllically-actlve polyether accordlng to the followlng general formulae:
C 0-A-0~ ~2 ~ Y-A-Y
Formula II Formula III
whereln Y ls a non-nucleophlllc molety and A ls deflned above.
Solvolysls ls then performed on the product of thls reactlon, and lt ls lsolated by conventlonal technlques.
Polymerlzatlon of tetrahydrofuran (or tetrahydrofuran plus a mlnor amount of one or more catlonlcally polymerlzable cycllc ethers havlng from 2 to about 4 rlng carbon atoms) wlth a superacld anhydrlde (such as trlfluoromethanesulfonlc anhydrlde) followed by termlnatlon of the resultlng dl-catlonlcally actlve llnear polyethers by reactlon wlth sultable nltrogen-contalnlng nucleophlles, provldes novel lntermedlates wlth the followlng general formulae:
X3 ~-A-~ X~- 2 ~ X2~-A-NX2 Formula IV Formula V
whereln X and A are as deflned above. Sultable nitrogen-contalnlng nucleophlles are those havlng no actlve hydrogens.
Solvolysls of the novel lntermedlates provldes the purely prlmary dlamlno-termlnated polyethers. Chaln-extenslon of these polyethers then provldes the purely llnear polyether-polyurea block copolymers.
There ls dlsclosed a method for the preparatlon of purely prlmary dlamlno polyethers of Formula I:
4d 60557-3450 Formula I
where A ls a polyether molety of molecular welght above about 3500 contalning recurrlng groups, a ma~or portlon conslstlng of oxytetramethylene unlts, and at most a mlnor portlon conslstlng of other oxyalkylene unlts, the alkyl portlons thereof havlng up to about 4 stralght chaln carbon atoms. Preferably, A conslsts excluslvely of oxytetramethylene unlts. Preferred dlamlno polyethers are a- ~-dlamlnopolytetramethylene oxldes havlng the followlng formula: / \
H2N ~ '~ '~~NH2 n Formula IA
whereln n ls an lnteger of at least about 50, preferably from about 140 to about 280.
The method conslsts of the hydrolysls or, preferably, methanolysls of the novel lntermedlates represented by Formulas IV
and V;
X ~-A-~NX ' 2 ~ X2N-A-NX2 Formula IV Formula V
where X ls a substltuent whlch ls readlly cleaved wlth hydroxyllc solvent such as water or, preferably, methanol to provlde the free amlne, and A ls as deflned above.
The novel intermediates of Formulas IV and V are made by reacting terminally electrophilically active polyethers corresponding to Formulas II and III:
Cd~ -- A --(3C~1 ' 2~ Y -- A -- Y
Formula II Formula III
where A is as defined above and wherein Y is a 10 non-nucleophilic moiety such as a trifluoromethanesulfonoxy group, a fluorosulfonoxy group, phosphorus hexafluoride, and the like, with a nitrogen nucleophile that has no active hydrogens. This nucleophile can be represented by Formula VI:
NX'X2 Formula VI
where X is a substituent which is easily cleaved by 20 hydroxylic solvents such as water or, preferably, methanol to provide the free amine; x~ may be the same as x or may be a pair of electrons to provide a negative charge. The polyethers of Formulas II and III are prepared by polymerization of tetrahydrofuran (or tetrahydrofuran plus up 25 to about 40 mole percent of one or more cationically polymerizable comonomeric cyclic ethers having from 2 to about 4 ring carbon atoms) with a superacid anhydride such as trifluoromethanesulfonic anhydride. ~xamples of cationically polymerizable cyclic ether comonomers include 30 3-methyltetrahydrofuran, 2-methyltetrahydrofuran, ethylene oxide, oxacyclobutane, and the like.
In order to obtain polyether amines by the method 'h^ procont in:~ntion~ the highly difunctional bis-electrophilically active polymer of Formula II or III is reacted with a suitable nitrogen containing nucleophile of Formula VI. This provides the novel intermediates of Formulas IV and V. Suitable nucleophiles are those which have no N-H
bonds. Utilizing such nucleophiles entirely eliminates the possibility of forming undesired secondary or tertiary amine in-chain moieties. The nucleophiles should also be reasonably soluble in non-hydroxylic solvents. The X groups, as stated 5 above, should be substituents which are readily cleaved with a solvent, such as water or, preferably, methanol, to provide the primary amine moiety, -NH2. Finally, the X substituent should be obtained in such a state as to be easily and completely removed from the diamino polyether endproduct.
Preferable nucleophiles include hexamethylene-tetramine and alkali metal salts of hexamethyldisilazane. The lithium salt is particularly preferred. Use of these nucleophiles result in the novel intermediates having the Formulas IVA and VA as depicted below:
N3(CH2)6N-A-N(CH2)6N3-2 Formula IVA
(Me3Si)2N-A-N(SiMe3)2 Formula VA
Cleavage of these intermediates to desired diprimary amines occurs readily upon heating with methanol, 25 or methanol and sulfuric acid. The byproducts of the methanolysis, dimethoxymethane and methoxytrimethylsilane, respectively, are highly volatile and easily distilled from the polymer solution.
The polyether diamines obtained by the method 30 ~b~ Rv-Rt~n are highly pure. High molecular weight polyether-polyurea block copolymers may be produced from the reaction of these diamines with various diisocyanates in stoichiometric molar ratios without gellation caused by crosslinking due to the presence of multifunctional 35 impurities. Preferred diisocyanates include toluene diisocyanate, hexamethylene diisocyanate, 4,4'-methylene-bis(phenylisocyanate), 4,4'-methylene-bis(cyclohexyl-isocyanate), and isophorone diisocyanate.
Preferred solvents for the chain extension reaction are those which are unreactive with isocyanates and which maintain both the reactants and the products in solution.
Preferred solvents include ethers, chlorinated hydrocarbons, S certain alcohols, and mixtures thereof. Most preferred solvents include methylene chloride, tetrahydrofuran and isopropanol.
Polyether-~olyurea block copolymers created by chain extension ofAdiprimary amines made by the method 10 thi~ inv~nt-ion are purely linear, and comprise a repeating unit represented by Formula VII as depicted below:
O O / O O~
li 11 11 11 N--Z--N-C- I_A_N_C N-Z- I_C_W_B_W_C
H H H H H H J
Formula VII
wherein:
20 Z is a divalent radical selected from phenylene, alkylene, aralkylene, and cycloalkylene; preferably Z is methylene dicyclohexylene, hexamethylene and methylene cyclohexylene;
B is a divalent radical selected from alkylene, aralkylene, cycloalkylene, and phenylene;
25 W is a difunctional moiety selected from -O- and -N- where D is hydrogen, an alkyl radical with from one to ten carbon atoms, phenyl, or an alkylene radical which completes a ring structure including B to form a heterocycle;
30 m is an integer from zero to about 25, preferably from about 2 to about 10; and A is as defined above.
The polymers are made by polymerizing in an inert atmosphere the exceptionally pure polyether diamine of 35 Formula I, optional diamine or diol chain extender having a molecular structure represented by Formula VIII:
~ w-~--w--i~
Fo rmula VI I I
5 where W and ~ are as defined above, and a stoichiometric amount of diisocyanate having a molecular structure represented by Formula IX:
OCN-Z-NCO
Fo rmula IX
where Z is as described above.
The combined molar ratio of polyether diamine and 15 diamine or diol chain extender to diisocyanate in the reaction is that which will provide useful properties in the final product, preferably about 1:0.95 to about 1:1.05.
The resulting polyether polyurea block copolymers are purely linear, high molecular weight, soluble elastomers 20 with outstanding properties. Such elastomers have many applications which are well known in the art. For a detailed discussion, see Polyurethanes: Chemistry and Technology, Part II, Saunders, J. ~. and Frisch, K.C., Interscience, NY 1964, pp. 431-447. Depending on the particular application, the 25 elastomeric properties can be varied significantly by the choice of molecular weight of the polyether diamine and, especially, by the incorporation of various low molecular weight chain extenders such as hexamethylene diamine, xylylene diamine, piperazine, and the like, with 30 1,3-di(4-piperidyl) propane being most preferred.
The following examples are intended to be illustrative only, and should not be construed as limiting the invention.
35Example 1 A 500 ml three-necked round bottom flask was charged with 125 g dry tetrahydrofuran and 25 g methylene ~ 3~0~ 94 chloride. The solution was cooled to 12C, and, with mechanical stirring, 3.3 g trifluoromethanesulfonicanhydride in 25 g methylene chloride was added rapidly via syringe.
After an exotherm to 21C, the reaction was cooled to 12C
and stirred at that temperature for 2.0 hours. The stirrer was stopped, and a slurry of 4.1 g hexamethylene tetramine in 25 g chloroform was added. The stirrer was started and run at high speed for 1/2 hour at room temperature. A solution of 9.3 g concentrated H2 S04 in 60 g methanol and 60 g toluene was added, the reaction was equipped with a distilling head, and the volatiles were distilled while replenishing the system with methanol until the pot temperature remained at 65C for one hour. A solution of 2.1 g hydroxylamine sulfate in 6 ml water was added and the reaction heated under reflux for an hour. The solution was then cooled to about 30C, and 29.0 g 50~ NaOH was added with stirring. The mixture was heated, and the MeOH and other volatiles were allowed to distill while replenishing the pot with toluene. At a pot temperature of 80C, 4.1 g solid NaHCO3 was added and the distillation continued until the pot reached 108C. The mixture was cooled to about 60-70C and filtered through a layer of a filter aid such as diatomaceous earth, available from Johns-Manville under the tradename Super Cel~, washing the collected salts with toluene. The combined filtrate and 25 washings were stripped to dryness on a rotary evaporator to provide 79.6 g (64%) polytetramethylene oxide diprimary amine as a clear, colorless, viscous oil which solidified on standing at room temperature. Titration of a sample in isopropanol-tetrahydrofuran solution with 0.1 N HCl to a bromphenol blue endpoint gave a molecular weight of 9,734.
Example 2 To a 1,000 ml three-necked round bottom flask under dry nitrogen was added 150 g dry tetrahydrofuran and 26.4 g cyclohexane. While stirring mechanically, 3.45 g (CF3SO2)20 was added rapidly via syringe at room temperature. The temperature was allowed to rise to 30C, and then the stirred ~f~ r1~
reaction was cooled to 15~C and held at that temperature for a total of 2 1/2 hours. At that time, 25 ml of a 1.0 M
solution of lithium bis(trimethylsilyl)amide in hexane was added rapidly via syringe. The temperature rose to 21C, the mixture was stirred at room temperature for 1/2 hour, and then diluted to 800 ml with toluene and 100 ml methanol. The reaction flask was fitted for distillation and the volatiles collected to a pot temperature of 110C while keeping the volume constant by the continued addition of toluene. The resulting solution, containing a precipitate of lithium trifluoromethanesulfonate, was cooled to 50-60C and filtered through a pad of Super CelR filter material which was washed with additional toluene. The combined filtrate and washings were stripped to dryness on a rotary evaporator to give polytetramethylene oxide diprimary amine as a pale yellow viscous oil which solidified to a cream colored solid on standing. The yield was 97.5 g (65%). Titration with 0.1 N HCl gave a molecular weight of 11,000.
Example 3 A 75 gallon stainless steel reactor was charged with 90.7 kg dry tetrahydrofuran and cooled to 16C with agitation. A solution of 1.5 kg trifluoromethanesulfonic anhydride in 6.8 kg of cyclohexane was added rapidly with stirring. Transfer was completed with an additional 6.8 kg of cyclohexane. The reaction exothermed to 32C and was then heated to 43C and held at this temperature for 1/2 hour. The reaction was cooled to 18-21C for an additional 2.5 hours.
The viscous, clear solution was treated as rapidly as possible with 13.3 kg of a 20% solution of lithium bis(trimethyl silyl) amide in hexane. The reaction exothermed to 27C and was allowed to stir for l/2 hour. Toluene (113.4 kg) and methanol (15.5 kg) were charged to the reactor and the heating jacket set to 88C. Volatiles were allowed to 35 distill over a two hour period. The jacket temperature was then raised to 149C and the distillation continued until the contents reached 104C. The solution was cooled to 32C;
45.q kg of heptane and 6.8 kg of Super Cel~ filter material were added. After stirring for 1/2 hour, the mixture was filtered and the filtrate returned to the kettle. A total of 83.9 kg of volatiles were distilled. The resulting solution 5 was cooled to room temperature to provide polytetramethylene oxide diprimary amine as a 50% solids solution. The total yield of polymer was 63.5 kg (70% yield) and had a titrated molecular weight of 16,000.
Example 4 To a 1,000 ml three-necked round bottom flask under dry nitrogen was added 135 g dry tetrahydrofuran, 13.8 g 3-methyl tetrahydrofuran, and 26.4 g cyclohexane. While stirring mechanically, 3.47 g (CF3 S2 )2 was added rapidly 15 via syringe at 10C. The temperature was allowed to rise to 40C, and then the reaction was stirred for 1/2 hour, cooled to 15C, and held at that temperature for a total of 2 hours.
At that time, 25 ml of a 1.0 M solution of lithium bis(trimethylsilyl)amide in hexane was added rapidly via 20 syringe. The temperature rose to 28C, the mixture was stirred at room temperature for 1/2 hour, and then diluted with 200 ml of toluene. The reaction flask was fitted for distillation and the volatiles collected to a pot temperature of 110C while keeping the volume constant by the continued 25 addition of toluene. The resulting solution, containing a precipitate of lithium trifluoromethanesulfonate, was cooled to 22C and 178 g of heptane added before filtering through a pad of Super Cel~ filter material which was washed with additional toluene. The combined filtrate and washings were 30 concentrated to 30% solids w/w. Then, 125 g of methanol was added, and the solution was heated to 105C while allowing the methanol and other volatiles to distill. The resultant solution was stripped to dryness on a rotary evaporator to give polyether diprimary amine as a pale yellow viscous oil 35 which solidified to a cream colored solid on standing. The yield was 112.5 g (76%). Titration with 0.1 N HCl gave a molecular weight of 11,853.
Example 5 A solution of 8.33 g of 8,333 molecular weight polytetramethylene oxide diprimary amine (1.0 mmol) and 5 0.288 g 2,5-dimethylpiperazine (1.0 mmol) in 65 g isopropanol and 35 g methylene chloride was stirred and treated with 0.786 g (2.0 mmol) of 4,4'-methylene bis(cyclohexyl-isocyanate) (H-MDI). In 15 minutes at room temperature, the viscosity had risen dramatically, but the solution remained 10 clear and did not gel. A film was cast to provide, after solvent evaporation, a clear, strong polyether polyurea elastomer film having the following properties:
Tensile - 8,155 psi Elongation - 660 Permanent Set - 12~
A film is completely soluble in solvents such as chloroform, toluene, isopropanol, and tetrahydrofuran.
Example 6 To a solution of 10.08 g of the polyether diprimary amine of Example 4 (11,853 molecular weight; 0.85 mmol) in 30 ml of methylene chloride at room temperature was added all at once with rapid stirring a solution of 0.76 g of isophorone diisocyanate (3.42 mmol). The resulting solution 25 was treated dropwise with stirring with a solution of 0.54 g 1,3-bis(4-piperidyl) propane (2.57 mmol) in 30 ml of methylene chloride. Toward the end of the addition, the reaction became quite viscous but remained clear. The contents of the flask were cast onto a glass plate and the 30 solvent allowed to evaporate. The resulting polyether-polyurea block copolymer was obtained as a clear, strong elastomeric film having the following properties:
Tensile - 5600 psi Elongation - 700%
Permanent Set - 35%
Claims (6)
1. A method for preparation of purely primary .alpha.,.omega.-diamino polyethers having the general formula H2N-A-NH2, wherein A is a polyether moiety having a molecular weight of at least about 3500 containing recurring groups, a major portion of which being oxytetramethylene units, and a minor portion being other oxyalkylene units having up to about 4 straight chain carbon atoms, comprising the steps of:
a) reacting a nitrogen-containing nucleophile accord-ing to the following formula:
NX'X2 where X is a substituent which is easily cleaved by hydroxylic solvents and X' is selected from the group consisting of X and an electron pair, with a terminally electrophilically active polyether represented by the following general formulae:
and Y - A - Y
wherein Y is a non-nucleophilic moiety, and A is as defined above;
b) performing solvolysis on the product of reaction a);
and c) isolating the products thereof.
a) reacting a nitrogen-containing nucleophile accord-ing to the following formula:
NX'X2 where X is a substituent which is easily cleaved by hydroxylic solvents and X' is selected from the group consisting of X and an electron pair, with a terminally electrophilically active polyether represented by the following general formulae:
and Y - A - Y
wherein Y is a non-nucleophilic moiety, and A is as defined above;
b) performing solvolysis on the product of reaction a);
and c) isolating the products thereof.
2. The method of claim 1 wherein A is polytetramethylene oxide.
3. The method of claim 1 wherein the nitrogen-containing nucleophile is selected from the group consisting of hexamethylene tetramine and the alkali metal salts of hexamethyldisilazane.
4. Novel intermediates for a purely primary .alpha.,.omega.-diamino polyether having the following general formulae:
and X2N-A-NX2 wherein X is a substituent which is easily cleaved by hydroxylic solvents, Y is a non-nucleophilic moiety and A is a polyether moiety of molecular weight above about 3500 containing recurring groups, a major portion of which being oxytetramethylene units, and a minor portion being other oxyalkylene units having up to about 4 straight chain carbon atoms.
and X2N-A-NX2 wherein X is a substituent which is easily cleaved by hydroxylic solvents, Y is a non-nucleophilic moiety and A is a polyether moiety of molecular weight above about 3500 containing recurring groups, a major portion of which being oxytetramethylene units, and a minor portion being other oxyalkylene units having up to about 4 straight chain carbon atoms.
5. The novel intermediates of claim 4 having the general formulae:
and (Me3Si)2N-A-N(SiMe3)2 wherein A is polytetramethylene oxide.
and (Me3Si)2N-A-N(SiMe3)2 wherein A is polytetramethylene oxide.
6. A purely primary .alpha.,.omega.-diamino polyether produced by the method of claim 1, 2 or 3.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA000616529A CA1329285C (en) | 1987-06-26 | 1992-12-03 | Method of making purely primary diamines |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US07/067,555 US4833213A (en) | 1987-06-26 | 1987-06-26 | Method of making purely primary diamines from nitrogen containing nocleophile and terminally electrophilically active polyether |
US067,555 | 1987-06-26 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA000616529A Division CA1329285C (en) | 1987-06-26 | 1992-12-03 | Method of making purely primary diamines |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1320494C true CA1320494C (en) | 1993-07-20 |
Family
ID=22076794
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA000568395A Expired - Fee Related CA1320494C (en) | 1987-06-26 | 1988-06-02 | Method of making purely primary diamines |
Country Status (6)
Country | Link |
---|---|
US (1) | US4833213A (en) |
EP (1) | EP0296852B1 (en) |
JP (2) | JP2543954B2 (en) |
KR (1) | KR0129110B1 (en) |
CA (1) | CA1320494C (en) |
DE (1) | DE3855056T2 (en) |
Families Citing this family (43)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02242822A (en) * | 1989-03-16 | 1990-09-27 | Hodogaya Chem Co Ltd | Production of polyoxyalkylene derivative |
US5013813A (en) * | 1989-12-18 | 1991-05-07 | Texaco Chemical Company | Polyurea elastomer with rapid dry time |
US5003107A (en) * | 1989-12-18 | 1991-03-26 | Texaco Chemical Company | Catalytic method for the reductive amination of poly(oxytetramethyle) glycols |
CA2079933A1 (en) * | 1991-11-04 | 1993-05-05 | Donald R. Hollingsworth | Catalytic method for the reductive amination of poly(oxytetramethylene) diacetates |
US5483008A (en) * | 1992-02-07 | 1996-01-09 | Research Development Corporation Of Japan | Polyether having heterofunctional groups at both ends, process for the preparation thereof and polymerization initiator therefor |
JP2593032B2 (en) * | 1992-02-07 | 1997-03-19 | 新技術事業団 | Heterofunctional polyethers at both ends, method for producing the polyethers and polymerization initiators |
JP2855419B2 (en) * | 1995-12-19 | 1999-02-10 | 帝国ピストンリング株式会社 | Combination oil ring spacer expander and combination oil ring |
CN1128170C (en) * | 1997-06-13 | 2003-11-19 | 美国3M公司 | Liquid pavement marking composation |
USRE40088E1 (en) | 1997-06-13 | 2008-02-19 | 3M Innovative Properties Company | Liquid pavement marking compositions |
DE10201903A1 (en) | 2002-01-19 | 2003-07-31 | Degussa | Molding compound based on polyether amides |
DE10228439A1 (en) | 2002-06-26 | 2004-01-22 | Degussa Ag | Plastic optical fiber |
DE102007011287A1 (en) | 2007-03-08 | 2008-09-11 | Evonik Degussa Gmbh | Tube useful as compressed-air brake line, comprises an outer layer made from a polymer melt, an intermediate layer made from adhesive polymer melt, and an interior layer made from polymer melt |
DE102007040683A1 (en) | 2007-08-29 | 2009-03-05 | Evonik Degussa Gmbh | Sheathed pipe |
EP2268486A2 (en) * | 2008-03-25 | 2011-01-05 | 3M Innovative Properties Company | Multilayer articles and methods of making and using the same |
WO2009120547A2 (en) | 2008-03-25 | 2009-10-01 | 3M Innovative Properties Company | Paint film composites and methods of making and using the same |
DE102009001001A1 (en) | 2009-02-19 | 2010-09-02 | Evonik Degussa Gmbh | Use of a conduit for the production of a pipeline laid in the water |
DE102010003909A1 (en) | 2010-04-13 | 2011-10-13 | Evonik Degussa Gmbh | Flexible tube with multilayer construction |
DE102010003917A1 (en) | 2010-04-13 | 2011-10-13 | Evonik Degussa Gmbh | Flexible tube with diffusion barrier |
DE102010028541A1 (en) | 2010-05-04 | 2011-11-10 | Evonik Degussa Gmbh | Composite of a polyamide molding compound and vulcanized elastomer |
DE102011007104A1 (en) | 2011-04-11 | 2012-10-11 | Evonik Degussa Gmbh | Polyamide sheathed steel construction tubes for offshore structures |
US8927737B2 (en) | 2011-08-09 | 2015-01-06 | Basf Se | Process for purifying ionic liquids |
DE102011090092A1 (en) | 2011-12-29 | 2013-07-04 | Evonik Degussa Gmbh | Process for the production of a molding from a polyamide molding compound with improved hydrolysis resistance |
DE102012207173A1 (en) | 2012-04-30 | 2013-10-31 | Evonik Degussa Gmbh | Coated metal object |
DE102012208020A1 (en) | 2012-05-14 | 2013-11-14 | Evonik Industries Ag | Method for producing a heatable tube |
DE102013205616A1 (en) | 2013-03-28 | 2014-10-02 | Evonik Industries Ag | Multilayer pipe with polyamide layer |
DE102013205614A1 (en) | 2013-03-28 | 2014-10-02 | Evonik Industries Ag | Method for producing a pipe lined with an inliner |
DE102013209126A1 (en) | 2013-05-16 | 2014-11-20 | Evonik Industries Ag | Air-brake line |
ES2874081T3 (en) | 2014-08-26 | 2021-11-04 | Evonik Operations Gmbh | Hydrolysis-stable polyamide blend |
EP3020277B1 (en) | 2014-11-12 | 2018-03-07 | Evonik Degussa GmbH | Composition with controlled release of biocidal metal ions |
EP3069876A1 (en) | 2015-03-17 | 2016-09-21 | Evonik Degussa GmbH | Laminate with one layer made of a partially aromatic polyamide |
EP3069866B1 (en) | 2015-03-20 | 2018-08-15 | Evonik Degussa GmbH | Heatable tube |
EP3477176A1 (en) | 2017-10-25 | 2019-05-01 | Evonik Degussa GmbH | Method for manufacturing a tube clad with an inner liner |
EP3640287A1 (en) | 2018-10-16 | 2020-04-22 | Röhm GmbH | Polyether blockamide poly(meth)acrylate foams |
JP7240859B2 (en) * | 2018-11-26 | 2023-03-16 | 株式会社カネカ | Method for producing purified polyether and method for producing curable composition |
DE102018133678A1 (en) | 2018-12-28 | 2020-07-02 | Evonik Operations Gmbh | Introduction of a data page into a value document |
CN114008092B (en) | 2019-06-13 | 2024-02-02 | 3M创新有限公司 | Cross-linking agent and curable composition comprising same |
CN116194541A (en) | 2020-08-11 | 2023-05-30 | 3M创新有限公司 | (meth) acrylate structural adhesives and methods |
US11739172B2 (en) | 2020-12-17 | 2023-08-29 | 3M Innovative Properties Company | Composition including monomer with a carboxylic acid group, monomer with a hydroxyl group, and crosslinker and related articles and methods |
WO2022264065A2 (en) | 2021-06-16 | 2022-12-22 | 3M Innovative Properties Company | Adhesive dispensing systems and methods |
CN117580878A (en) | 2021-06-29 | 2024-02-20 | 3M创新有限公司 | Pressure sensitive adhesives prepared using polyether-containing macromers |
WO2023052904A1 (en) | 2021-10-01 | 2023-04-06 | 3M Innovative Properties Company | Ultrasonic dispensing device |
WO2023105451A1 (en) | 2021-12-10 | 2023-06-15 | 3M Innovative Properties Company | Methods, systems, devices and kits for formulating structural adhesives |
WO2023105449A2 (en) | 2021-12-10 | 2023-06-15 | 3M Innovative Properties Company | Methods, systems, devices and kits for formulating structural adhesives |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3436359A (en) * | 1965-10-14 | 1969-04-01 | Minnesota Mining & Mfg | Polyether polyprimary polyamines and elastomeric products thereof |
US4181682A (en) * | 1978-01-09 | 1980-01-01 | Texaco Development Corp. | Aminated propoxylated polybutanediols |
DE3147736A1 (en) * | 1981-12-02 | 1983-06-09 | Bayer Ag, 5090 Leverkusen | METHOD FOR PRODUCING ELASTIC MOLDED BODIES |
GB2116966B (en) * | 1982-02-26 | 1986-01-15 | British Petroleum Co Plc | N-oxyalkylated aqueous compositions of quaternary ammenium salt surfactants |
US4451618A (en) * | 1982-09-29 | 1984-05-29 | The B. F. Goodrich Company | Block copolymers and process for their preparation |
-
1987
- 1987-06-26 US US07/067,555 patent/US4833213A/en not_active Expired - Lifetime
-
1988
- 1988-06-02 CA CA000568395A patent/CA1320494C/en not_active Expired - Fee Related
- 1988-06-23 EP EP88305728A patent/EP0296852B1/en not_active Expired - Lifetime
- 1988-06-23 DE DE3855056T patent/DE3855056T2/en not_active Expired - Fee Related
- 1988-06-24 JP JP63156632A patent/JP2543954B2/en not_active Expired - Lifetime
- 1988-06-24 KR KR1019880007661A patent/KR0129110B1/en not_active IP Right Cessation
-
1996
- 1996-03-12 JP JP8054744A patent/JP2720893B2/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
JPS6422921A (en) | 1989-01-25 |
JP2720893B2 (en) | 1998-03-04 |
JPH08253577A (en) | 1996-10-01 |
KR0129110B1 (en) | 1998-04-07 |
KR890000553A (en) | 1989-03-15 |
US4833213A (en) | 1989-05-23 |
EP0296852A3 (en) | 1990-06-06 |
JP2543954B2 (en) | 1996-10-16 |
EP0296852B1 (en) | 1996-03-06 |
DE3855056D1 (en) | 1996-04-11 |
DE3855056T2 (en) | 1996-10-31 |
EP0296852A2 (en) | 1988-12-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CA1320494C (en) | Method of making purely primary diamines | |
US3810874A (en) | Polymers prepared from poly(perfluoro-alkylene oxide) compounds | |
US3850856A (en) | Hydroxyl-ended epihalohydrin polymers by cationic polymerization | |
US9279035B2 (en) | Copolymers with perfluoropolyether segment and multiple aminooxalylamino groups | |
EP1728788B1 (en) | Fluorine-containing amide compound and method for preparing the same | |
US8907120B2 (en) | Perfluoropolyether-containing compounds with oxalylamino groups | |
US4933396A (en) | Method of making purely primary diamines | |
US5494990A (en) | Thermoplastic polyurethane resin having broad rubbery-state region and process for producing the same | |
CA1205234A (en) | Block copolymers and process for their preparation | |
US3172874A (en) | Xnxz xnx xnx | |
JPH0375557B2 (en) | ||
CA1329285C (en) | Method of making purely primary diamines | |
US6916894B2 (en) | Polydioxaborines | |
US4255561A (en) | Sulfide polymers of polyoxyalkylenes | |
US3637589A (en) | Method for preparing poly-carboranylenesiloxane polymers | |
US3207707A (en) | Nitrogen containing polymers | |
US6114528A (en) | Fluorinated amide compounds | |
US3162618A (en) | Poly-1, 2-alkylene oxaglycol carbamate and polymers thereof | |
US4182849A (en) | Copolymers made from divinyl aromatic compounds and alkylene polyamines | |
US5075503A (en) | Hydrazine terminated polyoxyalkylene amines | |
JP3325172B2 (en) | Organic fluorine compounds | |
US3464933A (en) | Novel c-n backbone polymers | |
US4129716A (en) | Urea-aldehyde resins | |
US3882122A (en) | Thienopyrazine dioxides and methods of making same | |
CA1136154A (en) | Polyphosphazene copolymers containing acetylenic substituents |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
MKLA | Lapsed |